Chiral organic molecular structures supported by planar surfaces

• Published in: The Journal of chemical physics 2023-12, Vol.159 (21)
• Main Authors: Savin, Alexander V., Kivshar, Yuri S.
• Format: Article
• Language: English
• Subjects: Boron nitride; Crystal lattices; Dynamic structural analysis; Flat surfaces; Hydrogen bonds; Isomers; Melting; Molecular dynamics; Molecular structure; Multilayers; Organic chemistry; Physics; Substrates
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0174859

We employ the molecular dynamics simulations to study the dynamics of acetanilide (ACN) molecules placed on a flat surface of planar multilayer hexagonal boron nitride. We demonstrate that the ACN molecules, known to be achiral in the three-dimensional space, become chiral after being placed on the substrate. Homochirality of the ACN molecules leads to stable secondary structures stabilized by hydrogen bonds between peptide groups of the molecules. By employing molecular dynamics simulations, we reveal that the structure of the resulting hydrogen-bond chains depends on the isomeric composition of the molecules. If all molecules are homochiral (i.e., with only one isomer being present), they form secondary structures (chains of hydrogen bonds in the shapes of arcs, circles, and spirals). If the molecules at the substrate form a racemic mixture, then no regular secondary structures appear, and only curvilinear chains of hydrogen bonds of random shapes emerge. A hydrogen-bond chain can form a zigzag array only if it has an alternation of isomers. Such chains can create two-dimensional (2D) regular lattices or 2D crystals. The melting scenarios of such 2D crystals depend on density of its coverage of the substrate. At 25% coverage, melting occurs continuously in the temperature interval 295–365 K. For a complete coverage, melting occurs at 415–470 K due to a shift of 11% of all molecules into the second layer of the substrate.